Chemistry: A Molecular Approach, 1st Ed.

Nivaldo Tro

Chapter 15
Acids and
Bases
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
2008, Prentice Hall
 Properties of Acids
•  sour taste
•  react with “active” metals
ü i.e., Al, Zn, Fe, but not Cu, Ag, or Au
2 Al + 6 HCl → 2 AlCl3 + 3 H2
ü corrosive
•  react with carbonates, producing CO2
ü marble, baking soda, chalk, limestone
CaCO3 + 2 HCl → CaCl2 + CO2 + H2O
•  change color of vegetable dyes
ü blue litmus turns red
•  react with bases to form ionic salts
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 Common Acids
Chemical Name Formula Uses Strength
Nitric Acid HNO3 explosive, fertilizer, dye, glue Strong
explosive, fertilizer, dye, glue,
Sulfuric Acid H2SO4 Strong
batteries
metal cleaning, food prep, ore
Hydrochloric Acid HCl Strong
refining, stomach acid
fertilizer, plastics & rubber,
Phosphoric Acid H3PO4 Moderate
food preservation
plastics & rubber, food
Acetic Acid HC2H3O2 Weak
preservation, Vinegar
Hydrofluoric Acid HF metal cleaning, glass etching Weak
Carbonic Acid H2CO3 soda water Weak
Boric Acid H3BO3 eye wash Weak
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 Structures of Acids
•  binary acids have acid hydrogens attached to
a nonmetal atom
ü HCl, HF

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 Structure of Acids
•  oxy acids have acid hydrogens attached to
an oxygen atom
ü H2SO4, HNO3

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 Structure of Acids
•  carboxylic acids have
COOH group
ü HC2H3O2, H3C6H5O7
•  only the first H in the
formula is acidic
ü the H is on the COOH

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 Properties of Bases
•  also known as alkalis
•  taste bitter
ü alkaloids = plant product that is alkaline
Ø often poisonous
•  solutions feel slippery
•  change color of vegetable dyes
ü different color than acid
ü red litmus turns blue
•  react with acids to form ionic salts
ü neutralization
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 Common Bases
Chemical Common
Formula Uses Strength
Name Name
sodium lye, soap, plastic,
NaOH Strong
hydroxide caustic soda petrol refining
potassium soap, cotton,
KOH caustic potash Strong
hydroxide electroplating
calcium
Ca(OH)2 slaked lime cement Strong
hydroxide
sodium
NaHCO3 baking soda cooking, antacid Weak
bicarbonate
magnesium milk of
Mg(OH)2 antacid Weak
hydroxide magnesia
detergent,
ammonium NH4OH, ammonia
fertilizer, Weak
hydroxide {NH3(aq)} water
explosives, fibers
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 Structure of Bases
•  most ionic bases contain OH ions
ü NaOH, Ca(OH)2
•  some contain CO32- ions
ü CaCO3 NaHCO3
•  molecular bases contain structures
that react with H+
ü mostly amine groups

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 Indicators
•  chemicals which change color depending on
the acidity/basicity
•  many vegetable dyes are indicators
ü anthocyanins
•  litmus
ü from Spanish moss
ü red in acid, blue in base
•  phenolphthalein
ü found in laxatives
ü red in base, colorless in acid
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 Arrhenius Theory
•  bases dissociate in water to produce OH- ions and
cations
ü ionic substances dissociate in water
NaOH(aq) → Na+(aq) + OH–(aq)
•  acids ionize in water to produce H+ ions and anions
ü because molecular acids are not made of ions, they cannot
dissociate
ü they must be pulled apart, or ionized, by the water
HCl(aq) → H+(aq) + Cl–(aq)
ü in formula, ionizable H written in front
HC2H3O2(aq) → H+(aq) + C2H3O2–(aq)
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 Arrhenius Theory

HCl ionizes in water, NaOH dissociates in water,

producing H+ and Cl– ions producing Na+ and OH– ions

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 Hydronium Ion
•  the H+ ions produced by the acid are so reactive they
cannot exist in water
ü H+ ions are protons!!
•  instead, they react with a water molecule(s) to produce
complex ions, mainly hydronium ion, H3O+
H+ + H2O → H3O+
ü there are also minor amounts of H+ with multiple water
molecules, H(H2O)n+

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 Arrhenius Acid-Base Reactions
•  the H+ from the acid combines with the OH-
from the base to make a molecule of H2O
ü it is often helpful to think of H2O as H-OH
•  the cation from the base combines with the
anion from the acid to make a salt
acid + base → salt + water
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
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 Problems with Arrhenius Theory
•  does not explain why molecular substances, like
NH3, dissolve in water to form basic solutions –
even though they do not contain OH– ions
•  does not explain how some ionic compounds, like
Na2CO3 or Na2O, dissolve in water to form basic
solutions – even though they do not contain OH–
ions
•  does not explain why molecular substances, like
CO2, dissolve in water to form acidic solutions –
even though they do not contain H+ ions
•  does not explain acid-base reactions that take place
outside aqueous solution
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 Brønsted-Lowry Theory
•  in a Brønsted-Lowry Acid-Base reaction, an
H+ is transferred
ü  does not have to take place in aqueous solution
ü  broader definition than Arrhenius
•  acid is H donor, base is H acceptor
ü  base structure must contain an atom with an
unshared pair of electrons
•  in an acid-base reaction, the acid molecule
gives an H+ to the base molecule
H–A + :B ⇔ :A– + H–B+
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 Brønsted-Lowry Acids
•  Brønsted-Lowry acids are H+ donors
ü any material that has H can potentially be a
Brønsted-Lowry acid
ü because of the molecular structure, often one H in
the molecule is easier to transfer than others
•  HCl(aq) is acidic because HCl transfers an H+ to
H2O, forming H3O+ ions
ü water acts as base, accepting H+

HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq)

acid base
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 Brønsted-Lowry Bases
•  Brønsted-Lowry bases are H+ acceptors
ü any material that has atoms with lone pairs can
potentially be a Brønsted-Lowry base
ü because of the molecular structure, often one atom
in the molecule is more willing to accept H+ transfer
than others
•  NH3(aq) is basic because NH3 accepts an H+
from H2O, forming OH–(aq)
ü water acts as acid, donating H+
NH3(aq) + H2O(l) ⇔ NH4+(aq) + OH–(aq)
base acid
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 Amphoteric Substances
•  amphoteric substances can act as either an
acid or a base
ü have both transferable H and atom with lone pair
•  water acts as base, accepting H+ from HCl
HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq)
•  water acts as acid, donating H+ to NH3
NH3(aq) + H2O(l) ⇔ NH4+(aq) + OH–(aq)

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 Brønsted-Lowry
Acid-Base Reactions
•  one of the advantages of Brønsted-Lowry theory
is that it allows reactions to be reversible
H–A + :B ⇔ :A– + H–B+
•  the original base has an extra H+ after the
reaction – so it will act as an acid in the reverse
process
•  and the original acid has a lone pair of electrons
after the reaction – so it will act as a base in the
reverse process
:A– + H–B+ ⇔ H–A + :B
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 Arrow Conventions
•  chemists commonly use two kinds
of arrows in reactions to indicate
the degree of completion of the
reactions
•  a single arrow indicates all the
reactant molecules are converted to
product molecules at the end
•  a double arrow indicates the
reaction stops when only some of
the reactant molecules have been
converted into products
ü ⇔ in these notes
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 Strong or Weak
•  a strong acid is a strong electrolyte
ü practically all the acid molecules ionize, →
•  a strong base is a strong electrolyte
ü practically all the base molecules form OH– ions,
either through dissociation or reaction with water, →
•  a weak acid is a weak electrolyte
ü only a small percentage of the molecules ionize, ⇔
•  a weak base is a weak electrolyte
ü only a small percentage of the base molecules form
OH– ions, either through dissociation or reaction with
water, ⇔
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 Strong Acids
•  The stronger the acid, the
more willing it is to donate H HCl → H+ + Cl-
HCl + H2O→ H3O+ + Cl-
ü use water as the standard base
•  strong acids donate
practically all their H’s
ü 100% ionized in water
ü strong electrolyte
•  [H3O+] = [strong acid]

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 Weak Acids
•  weak acids donate a small HF ⇔ H+ + F-
fraction of their H’s HF + H2O ⇔ H3O+ + F-
ü most of the weak acid
molecules do not donate H
to water
ü much less than 1% ionized
in water
•  [H3O+] << [weak acid]
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 Polyprotic Acids
•  often acid molecules have more than one ionizable H –
these are called polyprotic acids
ü the ionizable H’s may have different acid strengths or be equal
ü 1 H = monoprotic, 2 H = diprotic, 3 H = triprotic
Ø HCl = monoprotic, H2SO4 = diprotic, H3PO4 = triprotic
•  polyprotic acids ionize in steps
ü each ionizable H removed sequentially
•  removing of the first H automatically makes removal of
the second H harder
ü H2SO4 is a stronger acid than HSO4-

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 Strengths of Acids & Bases
•  commonly, acid or base strength is measured by
determining the equilibrium constant of a substance’s
reaction with water
HAcid + H2O ⇔ Acid-1 + H3O+1
Base: + H2O ⇔ HBase+1 + OH-1
•  the farther the equilibrium position lies to the products,
the stronger the acid or base
•  the position of equilibrium depends on the strength of
attraction between the base form and the H+
ü stronger attraction means stronger base or weaker acid

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 General Trends in Acidity
•  the stronger an acid is at donating H, the
weaker the conjugate base is at accepting H
•  higher oxidation number = stronger oxyacid
ü H2SO4 > H2SO3; HNO3 > HNO2
•  cation stronger acid than neutral molecule;
neutral stronger acid than anion
ü H3O+1 > H2O > OH-1; NH4+1 > NH3 > NH2-1
ü base trend opposite

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 Acid Ionization Constant, Ka
•  acid strength measured by the size of the
equilibrium constant when react with H2O
HAcid + H2O ⇔ Acid-1 + H3O+1
•  the equilibrium constant is called the acid
ionization constant, Ka
ü larger Ka = stronger acid
−1 +1
[Acid ] × [H 3O ]
Ka =
[HAcid]
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29
 Name Formula Ka1 Ka2 Ka3
Benzoic C6H5COOH 6.14 x 10-5
Propanoic CH3CH2COOH 1.34 x 10-5
Formic HCOOH 1.77 x 10-5
Acetic CH3COOH 1.75 x 10-5
Chloroacetic ClCH2COOH 1.36 x 10-5
Trichloroacetic Cl3C-COOH 1.29 x 10-4
Oxalic HOOC-COOH 5.90 x 10-2 6.40 x 10-5
Nitric HNO3 strong
Nitrous HNO2 4.6 x 10-4
Phosphoric H3PO4 7.52 x 10-3 6.23 x 10-8 2.2 x 10-13
Phosphorous H3PO3 1.00 x 10-2 2.6 x 10-7
Arsenic H3AsO4 6.0 x 10-3 1.05 x 10-7 3.0 x 10-12
Arsenious H3AsO3 6.0 x 10-10 3.0 x 10-14 very small
Perchloric HClO4 > 108
Chloric HClO3 5 x 102
Chlorous HClO2 1.1 x 10-2
Hypochlorous HClO 3.0 x 10-8
Boric H3BO3 5.83 x 10-10
Carbonic H2CO3 4.45 x 10-7 4.7 x 10-11
 Autoionization of Water
•  Water is actually an extremely weak electrolyte
ü therefore there must be a few ions present
•  about 1 out of every 10 million water molecules
form ions through a process called
autoionization
H2O ⇔ H+ + OH–
H2O + H2O ⇔ H3O+ + OH–
•  all aqueous solutions contain both H3O+ and OH–
ü the concentration of H3O+ and OH– are equal in water
ü [H3O+] = [OH–] = 10-7 M a 25°C
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 Ion Product of Water
•  the product of the H3O+ and OH–
concentrations is always the same number
•  the number is called the ion product of
water and has the symbol Kw
•  [H3O+] x [OH–] = Kw = 1 x 10-14 at 25°C
ü if you measure one of the concentrations, you
can calculate the other
•  as [H3O+] increases the [OH–] must
decrease so the product stays constant
ü inversely proportional
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 Acidic and Basic Solutions
•  all aqueous solutions contain both H3O+ and
OH– ions
•  neutral solutions have equal [H3O+] and [OH–]
ü [H3O+] = [OH–] = 1 x 10-7
•  acidic solutions have a larger [H3O+] than [OH–]
ü [H3O+] > 1 x 10-7; [OH–] < 1 x 10-7
•  basic solutions have a larger [OH–] than [H3O+]
ü [H3O+] < 1 x 10-7; [OH–] > 1 x 10-7

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 pH
•  the acidity/basicity of a solution is often
expressed as pH
•  pH = -log[H3O+], [H3O+] = 10-pH
ü exponent on 10 with a positive sign
ü pHwater = -log[10-7] = 7
ü need to know the [H+] concentration to find pH
•  pH < 7 is acidic; pH > 7 is basic, pH = 7 is
neutral

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 pH
•  the lower the pH, the more acidic the solution; the
higher the pH, the more basic the solution
ü 1 pH unit corresponds to a factor of 10 difference
in acidity
•  normal range 0 to 14
ü pH 0 is [H+] = 1 M, pH 14 is [OH–] = 1 M
ü pH can be negative (very acidic) or larger than 14
(very alkaline)

35
pH of Common Substances
Substance pH
1.0 M HCl 0.0
0.1 M HCl 1.0
stomach acid 1.0 to 3.0
lemons 2.2 to 2.4
soft drinks 2.0 to 4.0
plums 2.8 to 3.0
apples 2.9 to 3.3
cherries 3.2 to 4.0
unpolluted rainwater 5.6
human blood 7.3 to 7.4
egg whites 7.6 to 8.0
milk of magnesia (sat’d Mg(OH)2) 10.5
household ammonia 10.5 to 11.5
36
1.0 M NaOH 14
Tro, Chemistry: A Molecular Approach 37
 pOH
•  another way of expressing the acidity/basicity of
a solution is pOH
•  pOH = -log[OH-], [OH-] = 10-pOH
ü pOHwater = -log[10-7] = 7
ü need to know the [OH-] concentration to find pOH
•  pOH < 7 is basic; pOH > 7 is acidic, pOH = 7 is
neutral

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 Relationship between pH and pOH
•  the sum of the pH and pOH of a solution = 14.00
ü at 25°C
ü can use pOH to find pH of a solution

[ H 3O + ][OH - ] = K w = 1.0 × 10−14

(− log ([H O+ ][OH - ])) = − log (1.0 × 10−14 )
3
-
(− log ([H 3O ])) + (− log ([OH ])) = 14.00
+

pH + pOH = 14.00
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 Strong Bases
•  the stronger the base, the more
willing it is to accept H
ü use water as the standard acid
NaOH → Na+ + OH-
•  for strong bases, practically all
molecules are dissociated into
OH– or accept H’s
ü strong electrolyte
ü multi-OH strong bases
completely dissociated
•  [HO–] = [strong base] x (# OH)
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 Weak Bases
•  in weak bases, only a small
fraction of molecules accept H’s
ü weak electrolyte NH3 + H2O ⇔ NH4+ + OH-
ü most of the weak base molecules
do not take H from water
ü much less than 1% ionization in
water
•  [HO–] << [weak base]
•  finding the pH of a weak base
solution is similar to finding the
pH of a weak acid
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Tro, Chemistry: A Molecular Approach 42
 Structure of Amines

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 Acid-Base Properties of Salts
•  salts are water soluble ionic compounds
•  salts that contain the cation of a strong base and an
anion that is the conjugate base of a weak acid are
basic
ü NaHCO3 solutions are basic
Ø Na+ is the cation of the strong base NaOH
Ø HCO3− is the conjugate base of the weak acid H2CO3
•  salts that contain cations that are the conjugate acid of
a weak base and an anion of a strong acid are acidic
ü NH4Cl solutions are acidic
Ø NH4+ is the conjugate acid of the weak base NH3
Ø Cl− is the anion of the strong acid HCl

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 Metal Cations as Weak Acids
•  cations of small, highly charged metals are weakly
acidic
ü alkali metal cations and alkali earth metal cations pH neutral
ü cations are hydrated
Al(H2O)63+(aq) + H2O(l) ⇔ Al(H2O)5(OH)2+ (aq) + H3O+(aq)

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 Classifying Salt Solutions as
Acidic, Basic, or Neutral
•  if the salt cation is the counterion of a strong
base and the anion is the conjugate base of a
strong acid, it will form a neutral solution
ü NaCl Ca(NO3)2 KBr
•  if the salt cation is the counterion of a strong
base and the anion is the conjugate base of a
weak acid, it will form a basic solution
ü NaF Ca(C2H3O2)2 KNO2

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 Classifying Salt Solutions as
Acidic, Basic, or Neutral
•  if the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
strong acid, it will form an acidic solution
ü NH4Cl
•  if the salt cation is a highly charged metal ion
and the anion is the conjugate base of a strong
acid, it will form an acidic solution
ü Al(NO3)3

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 Classifying Salt Solutions as
Acidic, Basic, or Neutral
•  if the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
weak acid, the pH of the solution depends on the
relative strengths of the acid and base
ü NH4F since HF is a stronger acid than NH4+, Ka of
NH4+ is larger than Kb of the F−; therefore the
solution will be acidic

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 Polyprotic Acids
•  since polyprotic acids ionize in steps, each H has a
separate Ka
•  Ka1 > Ka2 > Ka3
•  generally, the difference in Ka values is great enough so
that the second ionization does not happen to a large
enough extent to affect the pH
ü most pH problems just do first ionization
ü except H2SO4 ⇒ use [H2SO4] as the [H3O+] for the second
ionization
•  [A2-] = Ka2 as long as the second ionization is
negligible
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50
 What Is Acid Rain?
•  natural rain water has a pH of 5.6
ü naturally slightly acidic due mainly to CO2
•  rain water with a pH lower than 5.6 is called
acid rain
•  acid rain is linked to damage in ecosystems and
structures

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 What Causes Acid Rain?
•  many natural and pollutant gases dissolved in the air
are nonmetal oxides
ü CO2, SO2, NO2
•  nonmetal oxides are acidic
CO2 + H2O ⇔ H2CO3
2 SO2 + O2 + 2 H2O ⇔ 2 H2SO4
•  processes that produce nonmetal oxide gases as waste
increase the acidity of the rain
ü natural – volcanoes and some bacterial action
ü man-made – combustion of fuel
•  weather patterns may cause rain to be acidic in regions
other than where the nonmetal oxide is produced
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